Stabilized organic material

ABSTRACT

o-Hydroxyphenyl-s-triazines of the formula I ##STR1## in which n is 1 to 4 and R 1  to R 7  are as defined in claim 1, can be used, in combination with sterically hindered amines of the polyalkylpiperidine type, for stabilizing organic polymers. Some of these compounds are novel and can also be used without polyalkylpiperidine.

This is a continuation of Ser. No. 07/978,064, filed on Nov. 18, 1992,which is a continuation of Ser. No. 07/611,207, filed on Nov. 8, 1990,which is a continuation-in-part of application Ser. No. 446,369, filedon Dec. 5, 1989, all now abandoned.

The present invention relates to an orgarnic material containing, asstabilizers, a mixture of a sterically hindered amine and ano-hydroxyphenyl-s-triazine, and to novel o-hydroxyphenyl-s-triazine.

It is already known from U.S. Pat. No. 4,619,956 that polymers can bestabilized against the action of light, moisture and oxygen by adding amixture of a sterically hindered amine and ano-hydroxyphenyl-s-triazine. The triazines used in this context containat least one phenyl group carrying a hydroxyl group in the o-position.

Triazine compounds of this type are relatively sparingly soluble in manysubstrates and tend to migrate. In accordance with the presentinvention, similar triazine derivatives which have an improvedcompatibility with or solubility in organic polymers are used.

The invention relates to an organic material which has been stabilizedagainst damage caused by light, heat and oxygen and which contains

(a) at least one sterically hindered amine of the polyalkylpiperidinetype and

(b) at least one o-hydroxyphenyl-s-triazine, wherein the triazinecompound (b) is a compound of the formula I ##STR2## in which n is 1 to4,

R₁ and R₂ independently of one another are H, OH, C₁ -C₁₂ alkyl,cyclohexyl or trifluoromethyl,

R₃ and R₄ independently of one another are H, OH, C₁ -C₁₂ alkyl,cyclohexyl, C₁ -C₁₈ -alkoxy or halogen and, in the event that n=1, canalso be a radical --OR₇,

R₅ and R₆ independently of one another are H, C₁ -C₁₂ alkyl or halogen,

R₇, if n is 1, is

a) C₁ -C₁₈ alkyl which is substituted by one or more of the groups OH,C₁ -C₁₈ alkoxy, C₃ -C₁₈ alkenoxy, halogen, phenoxy (which isunsubstituted or substituted by C₁ -C₁₈ alkyl, C₁ -C₁₈ alkoxy orhalogen), furyloxy, ##STR3## --COOH, --COOR₈, --CONH₂, --CONHR₉,--CON(R₉)(R₁₀), --NH₂, --NHR₉, --N(R₉)(R₁₀), --NHCOR₁₁, --CN and/or by--O--CO--R₁₁,

b) C₄ -C₅₀ alkyl which is interrupted by one or more O and can besubstituted by OH or/and glycidyloxy,

c) C₃ -C₆ alkenyl,

d) glycidyl or a group ##STR4## e) cyclohexyl which is unsubstituted orsubstituted by OH or --OCOR₁₁,

f) C₇ -C₁₁ phenylalkyl which is unsubstituted or substituted by OH, Clor CH₃,

g) --CO--R₁₂ or

h) --SO₂ --R₁₃,

and if n is 2, R₇ is

a) C₂ -C₁₆ alkylene,

b) C₄ -C₁₂ alkenylene,

c) xylylene,

d) C₃ -C₂₀ alkylene which is interrupted by one or more O and/orsubstituted by OH,

e) a group --CH₂ CH(OH)CH₂ O--R₁₅ --OCH₂ CH(OH)CH₂ --, --CO--R₁₆ --CO--,--CO--NH--R₁₇ --NH--CO-- or --(CH₂)_(m) --COO--R ₁₈ --OOC--(CH₂)_(m) --(in which m is 1 to 3) or ##STR5## and if n is 3, R₇ is a group ##STR6##and if n is 4, R₇ is a group ##STR7## R₈ is C₁ -C₁₈ alkyl, C₃ -C₁₈alkenyl, C₃ -C₂₀ alkyl which is interrupted by one or more O, N or Sand/or substituted by OH, C₁ -C₄ alkyl which is substituted by--P(O)(OR₁₄)₂, --N(R₉)(R₁₀) or --OCOR₁₁ and/or OH, C₃ -C₁₈ alkenyl,glycidyl or C₇ -C₁₁ phenylalkyl,

R₉ and R₁₀ independently of one another are C₁ -C₁₂ alkyl, C₃ -C₁₂alkoxyalkyl, C₄ -C₁₆ dialkylaminoalkyl or C₅ -C₁₂ cycloalkyl, or R₉ andR₁₀ together are C₃ -C₉ alkylene or C₃ -C₉ oxaalkylene or C₃ -C₉azaalkylene,

R₁₁ is C₁ -C₁₈ alkyl, C₂ -C₁₈ alkenyl or phenyl,

R₁₂ is C₁ -C₁₈ alkyl, C₂ -C₁₈ alkenyl, phenyl, C₁ -C₁₂ alkoxy, phenoxy,C₁ -C₁₂ alkylamino or C₆ -C₁₂ arylamino or a group --R₂₄ --COOH or--NH--R₁₇ --NCO,

R₁₃ is C₁ -C₁₂ alkyl, C₆ -C₁₂ aryl or C₇ -C₁₄ alkaryl,

R₁₄ is C₁ -C₁₂ alkyl or phenyl,

R₁₅ is C₂ -C₁₀ alkylene, C₄ -C₅₀ alkylene which is interrupted by one ormore O, phenylene or a group -phenylene-X-phenylene- in which X is--O--, --S--, --SO₂ --, --CH₂ -- or --C(CH₃)₂ --,

R₁₆ is C₂ -C₁₀ alkylene, C₁ -C₁₀ oxaalkylene or C₂ -C₁₀ thiaalkylene, C₆-C₁₂ arylene or C₂ -C₆ alkenylene,

R₁₇ is C₂ -C₁₀ alkylene, phenylene, tolylene, diphenylenemethane or agroup ##STR8## R₁₈ is C₂ -C₁₀ alkylene or C₄ -C₂₀ alkyene which isinterrupted by one or more O,

R₁₉ is C₃ -C₁₂ alkanetriyl,

R₂₀ is C₄ -C₁₂ alkanetetryl,

R₂₃ is C₂ -C₁₀ alkylene, phenylene or a group ##STR9## wherein X is O,S, SO₂, CH₂ or C(CH₃)₂, and R₂₄ is C₂ -C₁₄ alkylene, vinylene oro-phenylene.

If one of the substitutents in formula I is C₁ -C₁₂ alkyl, it can beunbranched or branched alkyl, for example methyl, ethyl, propyl,isopropyl, n-butyl, i-butyl, s-butyl or t-butyl, pentyl, hexyl, heptyl,octyl, 2-ethylhexyl, di-t-octyl, nonyl, decyl, undecyl or dodecyl. As C₁-C₁₈ alkyl, R₈, R₁₁ and R₁₂ can additionally be, for example,tetradecyl, hexadecyl or octadecyl.

As C₁ -C₁₈ alkoxy, R₃ and R₄ are preferably C₁ -C₁₂ alkoxy. The alkoxyradical is preferably unbranched. Examples of these are methoxy, ethoxy,propoxy, butoxy, hexyloxy, octyloxy, decyloxy or dodecyloxy.

As substituted C₁ -C₁₂ alkyl, R₇ can be substituted by one or more ofthe groups OH, C₁ -C₁₈ alkoxy, halogen, phenoxy which is unsubstitutedor substituted by C₁ -C₁₈ alkyl, C₁ -C₁₈ alkoxy or halogen, --COOH,--COOR₈, --CONH₂, --CONHR₉, --CON(R₉)(R₁₀), --NH₂, --NHR₉,--NH(R₉)(R₁₀), --NHCOR₁₁, --CN or --OCOR₁₁. The following groups areexamples of such substituted alkyl groups: --CH₂ CH₂ OH, --CH₂CH(OH)CH₃, --CH₂ CH(OH)C₂ H₅, --CH₂ CH(OH)C₆ H₁₃, --CH₂ CH(OH)C₁₀ H₂₁,--CH₂ CH₂ OCH₃, --CH₂ CH₂ OC₂ H₅, --CH₂ CH₂ OC₄ H₉, --(CH₂)₃ OH, --CH₂CH(OH)CH₂ OC₄ H₉, --CH₂ CH(OH)CH₂ OC₁₂ H₂₅, --CH₂ CH₂ Ophenyl, --CH₂ CH₂Cl, --CH₂ CH(OH)CH₂ Ophenyl, ##STR10## --CH₂ COOH, --CH₂ CH₂ COOH, --CH₂COOC₂ H₅, --CH₂ COOC₈ H₁₇, --CH₂ CH₂ COOCH₃, --CH₂ CH₂ COOC₄ H₉, --CH₂CH₂ COOC₁₂ H₂₅, --CH₂ CONH₂, --CH₂ CONHC₄ H₉, --CH₂ CON(C₄ H₉)₂, --CH₂CH₂ CONHC₁₂ H₂₅, --CH₂ CH₂ CON(C₂ H₅)₂, --CH₂ CH₂ NH₂, --CH₂ CH₂N(CH₃)₂, --(CH₂)₃ --NH₂, --(CH₂)₃ --NHC₄ H₉, --(CH₂)₃ N(CH₃)₂, --(CH₂)₃N(C₂ H₅)₂, --(CH₂)₃ NHCOCH₃, --(CH₂)₃ NHCOC₇ H₁₅, --CH₂ CH₂ CN, --CH₂CH₂ OCOC₃ H₇, --CH₂ CH₂ OCOC₁₇ H₃₅, --CH₂ CH(CH₃)--OCOCH₃, --CH₂CH(OCOCH₃)CH₂ OC₈ H₁₇ or --CH₂ CH(OCOC₇ H₁₅)CH₂ Ophenyl.

As C₃ -C₆ alkenyl, R₇ can, for example, be allyl, methallyl or2-butenyl. As C₃ -C₁₈ alkenyl, R₈ can additionally also be, for example,octenyl, dodecenyl or oleyl. As C₂ -C₁₈ alkenyl, R₁₁ and R₁₂ canadditionally also be vinyl.

As C₇ -C₁₁ phenylalkyl which is unsubstituted or substituted by OH, Clor CH₃, R₇ and R₈ can, for example, be phenylethyl,2-hydroxy-2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 4-chlorobenzylor 4-methylbenzyl, but especially benzyl.

As C₂ -C₁₆ alkylene, R₇ can be unbranched or branched alkylene, forexample di-, tri-, tetra-, hexa-, octa-, deca- or dodeca-methylene,2,2-dimethyl-prop-1,3-ylene or 1,2-propylene. As C₄ -C₁₂ alkenylene, R₇can, in particular, be 2-buten-1,4-ylene. As C₃ -C₂₀ alkylene which isinterrupted by O and/or substituted by OH, R₇ can, for example, be oneof the groups --CH₂ CH(OH)CH₂ --, --CH₂ CH₂ OCH₂ CH₂ -- or --CH₂CH(OH)CH₂ O--(CH₂)_(x) --OCH₂ CH(OH)CH₂ -- in which x=2-10.

As C₃ -C₂₀ alkyl which is interrupted and/or substituted by OH, R₈ can,in particular, be alkyl which is substituted by OH or alkyl which isinterrupted by O and substituted by OH. Examples of these are the groups--CH₂ CH₂ OH, --CH₂ CH(OH)CH₃, --CH₂ CH(OH)C₆ H₁₃, --CH₂ CH₂ OC₄ H₉,--CH₂ CH₂ OCH₂ CH₂ OH or --CH₂ CH₂ (OCH₂ CH₂)_(p) OH in which p=2-9.

As C₁ -C₄ alkyl which is substituted by --P(O)(OR₁₄)₂, --N(R₉)(R₁₀) or--OCOR₁₁, R₈ can, for example, be --CH₂ CH₂ P(O)(OC₂ H₅)₂, --CH₂P(O)(OC₆ H₁₃)₂, --CH₂ CH₂ N(CH₃)₂, --CH₂ CH₂ CH₂ N(C₂ H₅)₂, --CH₂ CH₂OCOC₇ H₁₅ or --CH₂ CH₂ OCOCH═CH₂.

As C₃ -C₁₂ alkoxyalkyl, R₉ and R₁₀ can, in particular, be 2-(C₁ -C₁₀alkoxy)-ethyl, for example 2-methoxyethyl, 2-butoxyethyl or2-octyloxyethyl. As C₄ -C₁₆ dialkylaminoalkyl, R₉ and R₁₀ can, forexample, be 2-dibutylaminoethyl, 2-diethylaminoethyl or3-dimethylaminopropyl.

As C₅ -C₁₂ cycloalkyl, R₉ and R₁₀ can, for example, be cyclopentyl,cyclooctyl or cyclododecyl, but especially cyclohexyl. If R₉ and R₁₀together are C₃ -C₉ alkylene, C₃ -C₉ oxaalkylene or C₃ -C₉ azaalkylene,they form, together with the N atom to which they are attached, aheterocyclic ring, for example a pyrrolidine, piperidine,2,6-dimethylpiperidine, morpholine, dimethylmorpholine or piperazinering.

As C₁ -C₁₂ alkoxy, R₁₂ can, for example, be methoxy, ethoxy, butoxy,hexyloxy, octyloxy, decyloxy or dodecyloxy.

As C₁ -C₁₂ alkylamino or C₆ -C₁₂ arylamino, R₁₂ can, for example, behexylamino, dodecylamino, phenylamino, naphthylamino or biphenylylamino.

As C₂ -C₁₀ alkylene, R₁₆, R₁₇ and R₁₈ can be unbranched or branchedalkylene, for example 1,2-ethylene, tri-, tetra-, penta-, hexa-, octa-or deca-methylene, 1,2-propylene or 2,2-dimethyltrimethylene, while asoxaalkylene or thiaalkylene, R₁₆ can, for example, be 2-oxatrimethylene,3-oxapentamethylene, 3-thiapentamethylene or 2-thiatrimethylene. As C₂-C₆ alkenylene, R₁₆ can, in particular, be --CH═CH--.

As C₆ -C₁₂ arylene, R₁₆ and R₁₇ can, for example, be phenylene,naphthylene or biphenylene. As C₇ -C₁₅ alkylarylene, R₁₇ can, inparticular, be tolylene.

As C₄ -C₂₀ alkylene which is interrupted by O, R₁₈ can be interrupted by1-9 O atoms and can, in particular, be the divalent radical formed byremoving the two hydroxyl groups from a polyethylene glycol orpolypropylene glycol.

In the substituents, aryl on its own or in combined radicals ispreferably phenyl, naphthyl or biphenylyl.

Compounds of the formula I which are preferred as the component (b) arethose in which n is 1 to 4, R₁ and R₂ independently of one another areH, OH or C₁ -C₄ alkyl, R₃ and R₄ independently of one another are H, OH,C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen or a radical --OR₇, R₅ and R₆independently of one another are H or C₁ -C₄ alkyl, R₇, if n is 1, is

a) C₁ -C₁₈ alkyl which is substituted by one or more of the groups OH,C₁ -C₁₈ alkoxy, allyloxy, phenoxy, furyloxy, ##STR11## --COOR₈,--CON(R₉)(R₁₀) and/or by --OCOR₁₁, b) C₄ -C₅₀ alkyl which is interruptedby one or more O and can be substituted by OH or/and glycidyloxy,

c) allyl, glycidyl or benzyl,

d) cyclohexyl or hydroxycyclohexyl,

and if n is 2, R₇ is C₄ -C₁₂ alkylene, C₄ -C₆ alkenylene, xylylene, C₃-C₂₀ alkylene which is interrupted by one or more O and/or substitutedby OH, or R₇ is a group --CH₂ CH(OH)CH₂ O--R₁₅ --OCH₂ CH(OH)CH₂ --,--CO--R₁₆ --CO--, --CH₂ --COO--R₁₈ --OOC--CH₂ -- or ##STR12## and if nis 3, R₇ is a group ##STR13## and if n is 4, R₇ is a group ##STR14## R₈is C₁ -C₁₂ alkyl, C₃ -C₁₈ alkenyl, C₃ -C₂₀ alkyl which is interrupted byone or more O and/or substituted by OH or R₈ is C₁ -C₄ alkyl which issubstituted by --P(O)(OR₁₄)₂,

R₉ and R₁₀ are C₁ -C₆ alkyl or R₉ and R₁₀ together are pentamethylene or3-oxapentamethylene,

R₁₁ is C₁ -C₁₂ alkyl, C₂ -C₅ alkenyl or phenyl,

R₁₄ is C₁ -C₄ alkyl,

R₁₅ is C₂ -C₈ alkylene, C₄ -C₅₀ alkylene which is interrupted by one ormore O, or is a group ##STR15## R₁₆ is C₂ -C₈ alkylene, C₂ -C₆oxaalkylene or C₂ -C₆ thiaalkylene and R₁₈ is C₄ -C₈ alkylene or C₄ -C₁₂alkylene which is interrupted by one or more O.

R₁ and R₂ are preferably hydrogen, chlorine or C₁ -C₄ alkyl,particularly hydrogen or methyl. R₃ and R₄ are preferably hydrogen,chlorine or C₁ -C₄ alkyl, particularly hydrogen, chlorine or methyl. R₅and R₆ are preferably hydrogen.

Compounds of the formula I which are particularly preferred as component(b) are those in which n is 1, 2 or 4, R₁ and R₂ independently of oneanother are H or CH₃, R₃ and R₄ independently of one another are H, CH₃or Cl, R₅ and R₆ are hydrogen, R₇, if n is 1, is

a) C₁ -C₁₄ alkyl which is substituted by one or more of the groups OH,C₁ -C₁₅ alkoxy, allyloxy, phenoxy, furyloxy, ##STR16## --COOR₈,--CON(R₉)(R₁₀) and/or by --OCOR₁₁, b) C₆ -C₄₅ alkyl which is interruptedby one or more O and can be substituted by OH or/and glycidyloxy,

c) glycidyl or

d) hydroxycyclohexyl,

and if n is 2, R₇ is C₆ -C₁₂ alkylene, 2-butenylene-1,4, xylylene, C₃-C₂₀ alkylene which is interrupted by one or more O or substituted byOH, or R₇ is a group --CH₂ CH(OH)CH₂ O--R₁₅ --OCH₂ CH(OH)CH₂ --,--CO--R₁₆ --CO--, --CH₂ --COO--R₁₈ --OOC--CH₂ -- or ##STR17## and if nis 4, R₇ is ##STR18## R₈ is C₄ -C₁₀ alkyl, oleyl, C₃ -C₂₀ alkyl which isinterrupted by one or more O and/or substituted by OH, or R₈ is --CH₂P(O)(OR₁₄)₂,

R₉ and R₁₀ are C₂ -C₆ alkyl

R₁₁ is C₆ -C₁₀ alkyl, C₂ -C₃ alkenyl

R₁₄ is C₁ -C₄ alkyl,

R₁₅ is C₂ -C₈ alkylene, C₁₀ -C₄₅ alkylene which is interrupted by morethan one O, or is a group ##STR19## R₁₆ is C₄ -C₈ alkylene and R₁₈ is C₄-C₈ alkylene.

A further preferred group of compounds of the formula I is formed bythose in which n is 1 or 2 and, if n is 1, R₇ is a group --CH₂ CH(OH)CH₂--OR₂₁ in which R₂₁ is C₁ -C₁₈ alkyl, allyl, phenyl, furyl, C₆ -C₁₂-alkanoyl or C₃ -C₅ alkenoyl and, if n is 2, R₇ is a group --CH₂CH(OH)CH₂ O--R₁₅ --OCH₂ CH(OH)CH₂ -- in which R₁₅ is as defined above.

The following compounds are examples of individual compounds of theformula I ##STR20##

Some of the triazine derivatives of the formula I are known compounds.Many such compounds and also their preparation and their use as UVabsorbers for organic materials are described in U.S. Pat. Nos.3,244,708, 3,249,608 and 3,423,360. Their use in photographic materialsis described in U.S. Pat. No. 3,843,371.

Another fraction of the triazine derivatives constitutes novelcompounds. Compounds which are novel and are also a subject of thepresent invention are those of the formula Ia ##STR21## in which n is 1to 4,

R₁ and R₂ independently of one another are H, OH, C₁ -C₁₂ alkyl,cyclohexyl or trifluoromethyl,

R₃ and R₄ independently of one another are H, OH, C₁ -C₁₂ alkyl,cyclohexyl, C₁ -C₁₈ -alkoxy or halogen and in the event that n=1, canalso be a radical --OR₇,

R₅ and R₆ independently of one another are H, C₁ -CH₁₂ alkyl or halogen,

R₇, if n is 1, is

a) C₁ -C₁₂ alkyl which is substituted by phenoxy (which is unsubstitutedor substituted by C₁ -C₁₈ alkyl, C₁ -C₁₈ alkoxy or halogen) or by agroup --COOR₈, --CONH₂, --CONHR₉, --CON(R₉)(R₁₀), --NH₂, NHR₉,--N(R₉)(R₁₀) or --O--CO--R₂₂,

b) C₄ -C₅₀ alkyl which is interrupted by more than one O and can besubstituted by OH or/and glycidyloxy, be substituted by OH or/andglycidyloxy,

c) glycidyl or a group ##STR22## d) cyclohexyl substituted by OH or--OCOR₁₁ e) a group --CH₂ CH(OH)CH₂ OR₂₁

f) a group --SO₂ --R₁₃,

g) a group --CO--R₁₂,

and if n is 2, R₇ is

a) C₂ -C₁₂ alkylene,

b) C₄ -C₁₂ alkenylene,

c) xylylene,

d) C₃ -C₂₀ alkylene which is interrupted by one or more O and/orsubstituted by OH,

e) a group --CH₂ CH(OH)CH₂ O--R₁₅ --OCH₂ CH(OH)CH₂ --, --(CH₂)_(m)--COO--R₁₈ --OOC--(CH₂)_(m) --(wherein m is 1-3) or ##STR23## and if nis 3, R₇ is a group ##STR24## (wherein m is 1-3), and if n is 4,

R₇ is a group ##STR25## (wherein m is 1-3), R₈ is C₃ -C₂₀ alkyl which isinterrupted by one or more O, N or S and can be substituted by OH, or R₈is C₁ -C₄ alkyl which is substituted by --P(O)(OR₁₄)₂, --N(R₉)(R₁₀), or--OCOR₁₁ and/or OH, or R₈ is C₃ -C₁₈ alkenyl, glycidyl or C₇ -C₁₁phenylalkyl,

R₉ and R₁₀ independently are C₁ -C₁₂ alkyl, C₃ -C₁₂ alkoxyalkyl, C₄ -C₁₆dialkylaminoalkyl or C₅ -C₁₂ cycloalkyl, or R₉ and R₁₀ together are C₃-C₉ alkylene or C₃ -C₉ -oxaalkylene or C₃ -C₉ azaalkylene,

R₁₁ is C₁ -C₁₈ alkyl, C₂ -C₁₈ alkenyl or phenyl,

R₁₂ is a group --R₂₄ --COOH or --NH--R₁₇ --NCO,

R₁₃ is C₁ -C₁₂ alkyl, C₆ -C₁₂ aryl or C₇ -C₁₄ alkaryl

R₁₄ is C₁ -C₁₂ alkyl or phenyl

R₁₅ is C₂ -C₁₀ alkylene, C₄ -C₅₀ alkylene which is interrupted by one ormore O, or R₁₅ is phenylene or a group -phenylene-X-phenylene- in whichX is --O--, --S--, --SO₂ --, --CH₂ -- or --C(CH₃)₂ --,

R₁₇ is C₂ -C₁₀ alkylene, phenylene, tolylene, diphenylenemethane or agroup ##STR26## R₁₈ is C₂ -C₁₀ alkylene or C₄ -C₂₀ alkylene which isinterrupted by one or more O,

R₁₉ is C₃ -C₁₂ alkanetriyl,

R₂₀ is C₄ -C₁₂ alkanetetryl,

R₂₁ is H, C₁ -C₁₈ alkyl, C₃ -C₁₈ alkenyl, phenyl, phenyl substituted byC₁ -C₁₂ alkyl, C₁ -C₁₂ alkoxy or halogen, or R₂₁ is C₂ -C₁₉ alkanoyl,benzoyl, C₃ -C₁₈ alkenoyl, furyl or a group ##STR27## R₂₂ is C₂ -C₅alkenyl, R₂₃ is C₂ -C₁₀ alkylene, phenylene or a group ##STR28## whereinX is O, S, SO₂, CH₂ or C(CH₃)₂, and R₂₄ is C₂ -C₁₄ alkylene, vinylene oro-phenylene.

Amongst these compounds of the formula Ia, preferred compounds are thosein which n is 1 to 4, R₁ and R₂ independently of one another are H, OHor C₁ -C₄ alkyl, R₃ and R₄ independently of one another are H, OH, C₁-C₄ alkyl, C₁ -C₄ alkoxy, halogen or a radical --OR₇, R₅ and R₆independently of one another are H or C₁ -C₄ alkyl,

R₇, if n is 1, is C₁ -C₆ alkyl which is substituted by --COOR₈,--COONHR₉, --CON(R₉)(R₁₀) or --OCOR₂₂, or R₇ is glycidyl,hydroxycyclohexyl or a group --CH₂ CH(OH)CH₂ OR₂₁, and if n is 2, R₇ isC₄ -C₁₂ alkylene, C₄ -C₆ alkenylene, xylylene, C₃ -C₂₀ alkylene which isinterrupted by one or more O and/or substituted by OH, or R₇ is a group--CH₂ CH(OH)CH₂ O--R₁₅ --OCH₂ CH(OH)CH₂ --, --CH₂ --COO--R₁₈ --OOCCH₂ --or ##STR29## and if n is 3, R₇ is a group ##STR30## and if n is 4, R₇ isa group ##STR31## R₈ is C₃ -C₂₀ alkyl which is interrupted by one ormore O and can be substituted by OH or

R₈ is C₁ -C₄ alkyl which is substituted by --P(O)(OR₁₄)₂ or R₈ is C₃-C₁₈ alkenyl,

R₉ and R₁₀ independently are C₁ -C₈ alkyl or cyclohexyl or R₉ and R₁₀together are pentamethylene or 3-oxapentamethylene,

R₁₄ is C₁ -C₁₄ alkyl,

R₁₅ is C₂ -C₈ alkylene, C₄ -C₅₀ alkylene which is interrupted by one ormore O, or R₁₅ is a group -phenylene-X-phenylene- in which X is --O--,--CH₂ -- or --C(CH₃)₂ --,

R₁₈ is C₄ -C₈ alkylene or C₄ -C₁₂ alkylene which is interrupted by oneor more O,

R₂₁ is H, C₄ -C₁₈ alkyl, allyl, phenyl, furyl, C₅ -C₁₉ alkanoyl or C₃-C₅ alkenoyl

and R₂₂ is C₂ -C₅ alkenyl, in particular those in which n is 1, 2 or 4,R₁ and R₂ independently of one another are H or CH₃, R₃ and R₄independently of one another are H, CH₃ or Cl, R₅ and R₆ are hydrogen,

R₇, if n is 1, is C₁ C₄ alkyl which is substituted by --COOR₈,--CON(R₉)(R₁₀) or --O--COR₂₂, or R₇ is glycidyl, 2-hydroxycyclohexyl ora group --CH₂ CH(OH)CH₂ OR₂₁, and if n is 2, R₇ is C₆ -C₁₂ alkenylene,2-butene-1,4-ylene, xylylene or C₃ -C₂₀ alkylene which is interrupted byone or more O and/or substituted by OH, or R₇ is a group --CH₂ CH(OH)CH₂O--R₁₅ --OCH₂ CH(OH)CH₂ --, --CH₂ --COO--R₁₈ --OOCCH₂ -- or ##STR32##and if n is 4, R₇ is a group ##STR33## R₈ is C₃ -C₂₀ alkyl which isinterrupted by one or more O and can be substituted by OH or

R₈ is --CH₂ P(O)(OR₄)₂ or oleyl

R₉ and R₁₀ are C₂ -C₆ alkyl

R₁₅ is C₂ -C₈ alkylene, C₁₀ C₄₅ alkylene which is interrupted by one ormore O or is a group ##STR34## R₁₈ is C₄ -C₈ alkylene, R₂₁ is H, C₄ -C₁₅alkyl, allyl, phenyl, furyl, C₅ -C₁₂ alkanoyl or C₃ -C₅ alkenoyl

and R₂₂ is C₂ -C₃ alkenyl.

The compounds of the formula Ia in which n is 2 are also preferred.

In general, the compounds of the formula I and Ia can be prepared byintroducing the radical R₇ into the p-hydroxyl group in a compound ofthe formula II ##STR35##

The compounds of the formula II are known compounds and can be preparedby a Friedel-Crafts reaction between cyanuric chloride and 1 mole of anaromatic compound of the formula ##STR36## and 1 mole of an aromaticcompound of the formula ##STR37## and 1 mole of resorcinol, asdescribed, for example, in Swiss Patent 480,091 or in Swiss Patent484,695 or in U.S. Pat. No. 3,244,708.

The conversion of II into I can be effected by various processes knownper se, depending on the nature of the radical R₇. If R₇ is substitutedalkyl, alkenyl, glycidyl, phenylalkyl, --CO--R₁₂, --SO₂ --R₁₃, alkylene,alkenylene, xylylene or --COR₁₆ CO--, the compound II or an alkali metalsalt thereof can be reacted with a halogen compound of the formulaHal-R₇ or Hal-R₇ -Hal in which Hal is chlorine, bromine or iodine, inparticular with the compounds Cl--R₇ and Cl--R₇ --Cl.

If R₇ is a group ##STR38## in which R' is hydrogen or CH₃ and Y is--COOR₈, --CONH₂, --CONHR₉, --CON(R₉)(R₁₀) or --CN, the compounds can beprepared by teacring a compound of the formula II with a compound of theformula ##STR39## in the manner of a so-called Michael additionreaction.

If R₇ is a group --CH₂ CH(OH)--W in which W is alkyl, phenyl,phenylalkyl or --CH₂ OR₂₁, such compounds can be prepared by reacting acompound of the formula II with an epoxide of the formula ##STR40##Analogously, compounds of the formula I in which n is 2 and R₇ is agroup --CH₂ CH(OH)CH₂ O--R₁₅ --OCH₂ CH(OH)CH₂ --, can be prepared byreacting 2 moles of a compound II and 1 mole of a bis-glycidyl ether ofthe formula ##STR41##

Compounds of the formula I in which R₇ is cyclohexyl substituted by OHcan be prepared by reaction of H with cyclohexene oxide.

Compounds of the formula I in which n is 2 and R₇ is --CO--NH--R₁₇--NH--CO-- can be prepared by reacting 2 moles of a compound of theformula II with 1 mole of a diisocyanate OCN--R₁₇ --NCO. Compounds ofthe formula I in which n is 2 and R₇ is a group --CH₂ CH(OH)CH₂ -- canbe prepared by reacting 2 moles of a compound II with 1 mole ofepichlorohydrin.

Compounds of formula I or Ia wherein n is 1 and R₇ is a group ##STR42##or a group --CO--R₂₄ --COOH or --CONH--R₁₇ --NCO can be prepared from IIby reaction with one molar equivalent of a compound ##STR43## orOCN--R₁₇ --NCO respectively.

It is also possible to convert a compound of the formula I into anothercompound of the formula I. For example, a hydroxyalkyl or aminoalkylradical R₇ can be converted by acylation with R₁₁ COCl into thecorresponding acyloxy or acylarnino derivative.

Or a cyanoalkyl radical R₇ can be converted by reduction into anaminoalkyl radical. Compounds in which R₇ is alkyl which is substitutedby --COOR₈ can be transesterified with another alcohol or polyol.

The methods required for the individual stages of the synthesis areknown to those skilled in the art; some of them are described in greaterdetail in the examples which follow later.

The polyalkylpiperidines used as the component (a) preferably contain atleast one group of the formula ##STR44## in which R is hydrogen ormethyl. R is preferably hydrogen. These are derivatives ofpolyalkylpiperidines, in particular of 2,2,6,6-tetramethylpiperidine.These compounds preferably carry one or two polar substituents or apolar spiro ring system in the 4-position of the piperidine ring. Thesecompounds can be low-molecular or oligomeric or polymeric compounds.

The following classes of polyalkylpiperidines are of particularimportance.

a) Compounds of the formula III ##STR45## in which n is a number from 1to 4, R is hydrogen or methyl, R₃₁ is hydrogen, amine oxide, hydroxyl,C₁ -C₁₂ alkyl, C₃ -C₈ alkenyl, C₃ -C₈ alkinyl, C₇ 1 -C₁₂ aralkyl, C₁-C₁₈ alkoxy, C₅ -C₈ cycloalkoxy, C₇ -C₉ phenylalkoxy, C₁ -C₈ alkanoyl,C₃ -C₅ alkenoyl, C₁ -C₁₈ alkanoyloxy, benzyloxy, glycidyl or a group--CH₂ CH(OH)--Z, in which Z is hydrogen, methyl or phenyl, R₃₁ beingpreferably H, C₁ -C₄ alkyl, allyl, benzyl, acetyl or acryloyl, and, if nis 1, R₃₂ is hydrogen, C₁ -C₁₈ alkyl which can be interrupted by one ormore oxygen atoms, cyanoethyl, benzyl, glycidyl, a monovalent radical ofan aliphatic, cycloaliphatic, araliphatic, unsaturated or aromaticcarboxylic acid, carbamic acid or an acid containing phosphorus or amonovalent silyl radical, preferably a radical of an aliphaticcarboxylic acid having 2 to 18 C atoms, a cycloaliphatic carboxylic acidhaving 7 to 15 C atoms, an α,β-unsaturated carboxylic acid having 3 to 5C atoms or an aromatic carboxylic acid having 7 to 15 C atoms, or, if nis 2, is C₁ -C₁₂ alkylene, C₄ -C₁₂ alkenylene, xylylene, a divalentradical of an aliphatic, cycloaliphatic, araliphatic or aromaticdicarboxylic acid, dicarbamic acid, or acid containing phosphorus, or adivalent silyl radical, preferably a radical of an aliphaticdicarboxylic acid having 2 to 36 C atoms, a cycloaliphatic or aromaticdicarboxylic acid having 8-14 C atoms or an aliphatic, cycloaliphatic oraromatic dicarbamic acid having 8-14 C atoms, or, if n is 3, is atrivalent radical of an aliphatic, cycloaliphatic or aromatictricarboxylic acid, an aromatic tricarbamic acid or an acid containingphosphorus, or a trivalent silyl radical, and, if n is 4, is atetravalent radical of an aliphatic, cycloaliphatic or aromatictetracarboxylic acid.

Examples of possible C₁ -C₁₂ alkyl substituents are methyl, ethyl,n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl,2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

As C₁ -C₁₈ alkyl, R₃₁ or R₃₂ can be the groups defined above andadditionally, for example, n-tridecyl, n-tetradecyl, n-hexadecyl orn-octadecyl.

As C₃ -C₈ alkenyl, R₃₁ can, for example, be 1-propenyl, allyl,methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl,4-tert-butyl-2-butenyl.

As C₃ -C₈ alkenyl, R₃₁ is preferably propargyl.

As C₇ -C₁₂ aralkyl, R₃₁ is especially phenethyl and, in particular,benzyl.

Examples of R₃₁ as C₁ -C₈ alkanoyl are formyl, propionyl, butyryl oroctanoyl, but preferably acetyl, and examples of R₂₁ as C₃ -C₅ alkenoylare especially acryloyl.

Examples of R₃₁ as C₁ -C₁₈ alkoxy are hexyloxy, heptyloxy, octyloxy ordecyloxy. As cycloalkoxy, R₃₁ is preferably cyclohexyloxy. Asphenylalkoxy, R₃₁ is preferably benzyloxy. Examples of R₃₁ asalkanoyloxy are acetoxy, butyroyloxy, hexanoyloxy, octanoyloxy,decanoyloxy or stearoyloxy.

Examples of R₃₂ as a monovalent radical of a carboxylic acid are aradical of acetic acid, caproic acid, stearic acid, acrylic acid,methacrylic acid, benzoic acid orβ-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid.

Examples of R₃₂ as a divalent radical of a dicarboxylic acid are aradical of malonic acid, succinic acid, glutaric acid, adipic acid,suberic acid, sebacic acid, maleic acid, itaconic acid, phthalic acid,dibutylmalonic acid, dibenzylmalonic acid,butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)-malonic acid orbicycloheptenedicarboxylic acid.

Examples of R₃₂ as a trivalent radical of a tricarboxylic acid are aradical of trimellitic acid, citric acid or nitrilocriacetic acid.

Examples of R₃₂ as a tetravalent radical of a tetracarboxylic acid arethe tetravalent radical of butane-1,2,3,4-tetracarboxylic acid orpyromellitic acid.

Examples of R₃₂ as a divalent radical of a dicarbamic acid are a radicalof hexamethylenedicarbamic acid or 2,4-toluylenedicarbamic acid.

Preferred compounds of the formula III are those in which R is hydrogen,R₃₁ is hydrogen or methyl, n is 1 and R₃₂ is C₁ -C₁₈ alkyl, or n is 2and R₃₂ is the diacyl radical of an alipharic dicarboxylic acid having4-12 C atoms.

The following compounds are examples of polyalkylpiperidine compounds ofthis class:

1) 4-Hydroxy-2,2,6,6-tetramethylpiperidine,

2) 1-Allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,

3) 1-Benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,

4) 1-(4-tert-Butyl-2-butenyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine,

5) 4-Stearoyloxy-2,2,6,6-tetramethylpiperidine,

6) 1-Ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine,

7) 4-Methacryloyloxy-1,2,2,6,6-pentamethylpiperidine,

8) 1,2,2,6,6-Pentamethylpiperidin-4-ylβ-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate,

9) Di-(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl) maleinate,

10) Di-(2,2,6,6-tetramethylpiperidin-4-yl) succinate,

11) Di-(2,2,6,6-tetramethylpiperidin-4-yl) glutarate,

12) Di-(2,2,6,6-tetramethylpiperidin-4-yl) adipate,

13) Di-(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,

14) Di-(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,

15) Di-(1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) sebacate,

16) Di-(1-allyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate,

17) 1-Hydroxy-4-β-cyanoethyloxy-2,2,6,6-tetramethylpiperidine,

18) 1-Acetyl-2,2,6,6-tetramethylpiperidin-4-yl acetate,

19) Tri--(2,2,6,6-tetramethylpiperidin-4-yl) trimellitate,

20) 1-Acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine,

21) Di-(2,2,6,6-tetramethylpiperidin-4-yl) diethylmalonate,

22) Di-(1,2,2,6,6-pentamethylpiperidin-4-yl) dibutylmalonate,

23)Di-(1,2,2,6,6-pentamethylpiperidin-4-yl)butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)-malonate,

24) Di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,

25) Di-(1-cyclhexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate,

26)Hexane-1',6'-bis-(4-carbamoyloxy-1-n-butyl-2,2,6,6-tetramethylpiperidine),

27)Toluene-2',4'-bis-(4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethylpiperidine),

28)Tetra-(2,2,6,6-tetramethylpiperidin-4-yl)butane-1,2,3,4-tetracarboxylate,

29)Tetra-(1,2,2,6,6-pentamethylpiperidin-4-yl)butane-1,2,3,4-tetracarboxylate

30) Tris-(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphite,

31) Tris-(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphate,

32) Phenyl- bis-(1,2,2,6,6-pentamethylpiperidin-4-yl)!phosphonate,

33) 4-Hydroxy-1,2,2,6,6-pentamethylpiperidine,

34) 4-Hydroxy-N-hydroxyethyl-2,2,6,6-tetramethylpiperidine,

35) 4-Hydroxy-N-(2-hydroxypropyl)-2,2,6,6-tetramethylpiperidine,

36) 1-Glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidine.

b) Compounds of the formula IV ##STR46## in which n is the number 1 or2, R and R₃₁ are as defined under a), R₃₃ is hydrogen, C₁ -C₁₂ alkyl, C₂-C₅ hydroxyalkyl, C₅ -C₇ cycloalkyl, C₇ -C₈ aralkyl, C₂ -C₁₈ alkanoyl,C₃ -C₅ alkenoyl, benzoyl or a group of the formula ##STR47## and, if nis 1, R₃₄ is hydrogen, C₁ -C₁₈ alkyl, C₃ -C₈ alkenyl, C₅ -C₇ cycloalkyl,C₁ -C₄ alkyl which is substituted by a hydroxyl, cyano, alkoxycarbonylor carbamide group, glycidyl or a group of the formula --CH₂ --CH(OH)--Zor of the formula --CONH--Z in which Z is hydrogen, methyl or phenyl orR₃₄ is a group --CO--CO--NH--(C₁ -C₁₈ alkyl); or, if n is 2, R₃₄ is C₂-C₁₂ alkylene, C₆ -C₁₂ arylene, xylylene, a --CH₂ --CH(OH)--CH₂ -- groupor a group --CH₂ --CH(OH)--CH₂ --O--D--O-- in which D is C₂ -C₁₀alkylene, C₆ -C₁₅ arylene or C₆ -C₁₂ -cycloalkylene or, provided thatR₃₃ is not alkanoyl, alkenoyl or benzoyl, R₃₄ can also be a divalentradical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid ordicarbamic acid or the group --CO--, or, if n is 1, R₃₃ and R₃₄ togethercan be the divalent radical of an aliphatic, cycloaliphatic or aromatic1,2-dicarboxylic or 1,3-dicarboxylic acid.

Possible C₁ -C₁₂ alkyl or C₁ -C₁₈ alkyl substituents are as alreadydefined under a).

Possible C₅ -C₇ cycloalkyl substituents are especially cyclohexyl,

As C₇ -C₈ aralkyl, R₃₃ is especially phenylethyl or, in particular,benzyl. As C₂ -C₅ hydroxyalkyl, R₃₃ is especially 2-hydroxyethyl or2-hydroxypropyl.

Examples of R₃₃ as C₂ -C₁₈ alkanoyl are propionyl, butyryl, octanoyl,dodecanoyl, hexadecanoyl or octadecanoyl, but preferably acetyl, andexamples of R₃₃ as C₃ -C₅ alkenoyl are especially acryloyl.

Examples of R₃₄ as C₂ -C₆ alkenyl are allyl, methallyl, 2-butenyl,2-pentenyl, 2-hexenyl or 2-octenyl.

Examples of R₃₄ as C₁ -C₄ alkyl which is substituted by a hydroxyl,cyano, alkoxycarbonyl or carbamide group are 2-hydroxyethyl,2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl,2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or2--(dimethylaminocarbonyl)-ethyl.

Examples of possible C₂ -C₁₂ alkylene substituents are ethylene,propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene,octamethylene, decamethylene or dodecamethylene.

Examples of possible C₆ -C₁₅ arylene substituents are o-, m- orp-phenylene, 1,4-naphthylene or 4,4'-biphenylene.

As C₆ -C₁₂ cycloalkylene, D is especially cyclohexylene.

Preferred compounds of the formula IV are those in which n is 1 or 2, Ris hydrogen, R₃₁ is hydrogen or methyl, R₃₃ is hydrogen, C₁ -C₁₂ alkylor a group of the formula ##STR48## and, in the event that n=1, R₃₄ ishydrogen or C₁ -C₁₂ alkyl and, in the event that n=2, R₃₄ is C₂ -C₈alkylene.

The following compounds are examples of polyalkylpiperidine compounds ofthis class:

37)N,N'-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-hexamethylene-1,6-diamine,

38)N,N'-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-hexamethylene-1,6-diacetamide

39) Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-amine,

40) 4-Benzoylamino-2,2,6,6-tetramethylpiperidine,

41) N,N'-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dibutyladipamide,

42)N,N'-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dicyclohexyl-2-hydroxypropylene-1,3-diamine,

43) N,N'-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-p-xylylenediamine,

44) N,N'-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-succindiamide,

45) N-(2,2,6,6-Tetramethylpiperidin-4-yl)-β-aminopropionic acid dodecylester,

46) The compound of the formula ##STR49## 47)N-(1-Octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-N'-dodecyl-oxalamide48) N-(2,2,6,6-Tetramethylpiperidin-4-yl)-α-dodecylsuccinimide,

49) 4-Methacrylamido-1,2,2,6,6-pentamethylpiperidine.

c) Compounds of the formula V, ##STR50## in which n is the number 1 or2, R and R₃₁ are as defined under a) and, if n is 1, R₃₅ is C₂ -C₈alkylene or C₂ -C₈ hydroxyalkylene or C₄ -C₂₂ acyloxyalkylene and, if nis 2, R₃₅ is the group (--CH₂)₂ C(CH₂ --)₂.

Examples of R₃₅ as C₂ -C₈ alkylene or C₂ -C₈ hydroxyalkylene areethylene, 1-methylethylene, propylene, 2-ethylpropylene or2-ethyl-2-hydroxymethylpropylene.

An example of R₃₅ as C₄ -C₂₂ acyloxyalkylene is2-ethyl-2-acetoxymethylpropylene.

The following compounds are examples of polyalkylpiperidine compounds ofthis class:

50) 9-Aza-8,8,10,10-tetramethyl-1,5-dioxaspiro 5.5!undecane,

51) 9-Aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro 5.5!undecane,

52) 8-Aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro 4.5!decane,

53) 9-Aza-3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro5.5!undecane,

54)9-Aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl-1,5-dioxaspiro5.5!undecane,

55)2,2,6,6-Tetramethylpiperidin-4-spiro-2'-(1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-spiro-4'"-(2'",2'",6'",6'"-tetramethylpiperidine).

d) Compounds of the formulae VIA, VIB and VIC ##STR51## in which n isthe number 1 or 2, R and R₃₁ are as defined under a), R₃₆ is hydrogen,C₁ -C₁₂ alkyl, allyl, benzyl, glycidyl or C₂ -C₆ alkoxyalkyl and, if nis 1, R₃₇ is hydrogen, C₁ -C₁₂ alkyl, C₃ -C₅ alkenyl, C₇ -C₉ aralkyl, C₅-C₇ cycloalkyl, C₂ -C₄ hydroxyalkyl, C₂ -C₆ alkoxyalkyl, C₆ -C₁₀ aryl,glycidyl or a group of the formula --(CH₂)_(p) --COO--Q or the formula--(CH₂)_(p) --O--CO--Q in which p is 1 or 2 and Q is C₁ -C₄ alkyl orphenyl, or, if n is 2, R₃₆ is C₂ -C₁₂ alkylene, C₄ -C₁₂ alkenylene, C₆-C₁₂ arylene, a group --CH₂ --CH(OH)--CH₂ --O--D--O--CH₂ --CH(OH)--CH₂-- in which D is C₂ -C₁₀ alkylene, C₆ -C₁₅ arylene or C₆ -C₁₂cycloalkylene, or a group --CH₂ CH(OZ')CH₂ --(OCH₂ --CH(OZ')CH₂)₂ inwhich Z' is hydrogen, C₁ -C₁₈ alkyl, allyl, benzyl, C₂ -C₁₂ alkanoyl orbenzoyl, T_(l) and T₂ independently of one another are hydrogen, C₁ -C₁₈alkyl or C₆ -C₁₀ aryl or C₇ -C₉ aralkyl each of which is unsubstitutedor substituted by halogen or C₁ -C₄ alkyl, or T₁ and T₂, together withthe C atom linking them, form a C₅ -C₁₂ cycloalkane ring.

Examples of possible C₁ -C₁₂ alkyl substituents are methyl, ethyl,n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl,2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

Examples of possible C₁ -C₁₈ alkyl substituents can be the groupsdefined above and also, for example, n-tridecyl, n-tetradecyl,n-hexadecyl or n-octadecyl.

Examples of possible C₂ -C₆ alkoxyalkyl substituents are methoxymethyl,ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl,ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl orpropoxypropyl.

Examples of R₃₇ as C₃ -C₅ alkenyl are 1-propenyl, allyl, methallyl,2-butenyl or 2-pentenyl.

As C₇ -C₉ aralkyl, R₃₇, T₁ and T₂ are especially phenethyl or, inparticular, benzyl. If T₁ abd T₂, together with the C atom, form acycloalkane ring, this can, for example, be a cyclopentane, cyclohexane,cyclodecane or cyclododecane ring

Examples of R₃₇ as C₂ -C₄ hydroxyalkyl are 2-hydroxyethyl,2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

As C₆ -C₁₀ aryl, R₃₇, T₁ and T₂ are especially phenyl, α-naphthyl orβ-naphthyl each of which is unsubstituted or substituted by halogen orC₁ -C₄ alkyl.

Examples of R₃₇ as C₂ -C₁₂ alkylene are ethylene, propylene,2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene,decamethylene or dodecamethylene.

As C₄ -C₁₂ alkenylene,. R₃₇ is especially 2-butenylene, 2-pentenylene or3-hexenylene.

Examples of R₃₇ as C₆ -C₁₂ arylene are o-, m- or p-phenylene,1,4-naphthylene or 4,4'-biphenylene.

Examples of Z' as C₂ -C₁₂ alkanoyl are propionyl, butyryl, octanoyl ordodecanoyl, but preferably acetyl.

As C₂ -C₁₀ alkylene, C₆ -C₁₅ arylene or C₆ -C₁₂ cycloalkylene, D is asdefined under b).

The following compounds are examples of polyalkylpiperidine compounds ofthis class:

56) 3-Benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro 4.5!decane-2,4-dione,

57) 3-n-Octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro4.5!decane-2,4-dione,

58) 3-Allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiro4.5!decane-2,4-dione,

59) 3-Glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro4.5!decane-2,4-dione,

60) 1,3,7,7,8,9,9-Heptamethyl-1,3,8-triazaspiro 4.5!decane-2,4-dione,

62) 2-Isopropyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro4.5!decane,

62) 2,2-Dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro4.5!decane,

63) 2,2,4,4-Tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro5.1.11.2!heneicosane,

64) 2-Butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxospiro 4.5!decane,

65) 8-Acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro4.5!decane-2,4-dione

or the compounds of the following formulae: ##STR52##

e) Compounds of the formula VII, ##STR53## in which n is the number 1 or2 and R₃₃ is a group of the formula ##STR54## in which R and R₃₁ are asdefined under a), E is --O-- or --NR₄₁ --, A is C₂ -C₆ alkylene or--(CH₂)₃ --O-- and x is the numbers 0 or 1, R₃₉ is identical with R₃₈ oris one of the groups --NR₄₁ R₄₂, --OR₄₃, --NHCH₂ OR₄₃ or --N(CH₂ OR₄₃)₂,R₄₀ is identical with R₃₈ or R₃₉, and, if n is 1, and if n is 2, is agroup -E-B-E- in which B is C₂ -C₆ alkylene which can be interrupted by--N(R₄₁)--, R₄₁ is C₁ -C₁₂ alkyl, cyclohexyl, benzyl or C₁ -C₄hydroxyalkyl or a group of the formula ##STR55## R₄₂ is C₁ -C₁₂ alkyl,cyclohexyl, benzyl or C₁ -C₄ hydroxyalkyl and R₄₃ is hydrogen, C₁ -C₁₂alkyl or phenyl or R₄₁ and R₄₂ together are C₄ -C₅ alkylene or C₄ -C₅oxaalkylene, for example ##STR56## or a group of the formula ##STR57##or R₄₁ and R₄₂ are each a group of the formula ##STR58##

Examples of possible C₁ -C₁₂ alkyl substituents are methyl, ethyl,n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl,2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

Examples of possible C₁ -C₄ hydroxyalkyl substituents are2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or4-hydroxybutyl.

Examples of A as C₂ -C₆ alkylene are ethylene, propylene,2,2-dimethylpropylene, tetramethylene or hexamethylene.

Examples of R₄₁ and R₄₂ together as C₄ -C₅ alkylene or oxaalkylene aretetramethylene, pentamethylene or 3-oxapentamethylene.

The compounds of the following formulae are examples ofpolyalkylpiperidine compounds of this class: ##STR59## f) Oligomeric orpolymeric compounds in which the recurring structural unit contains a2,2,6,6-tetraalkylpiperidine radical of the formula (I), in particularpolyesters, polyethers, polyamides, polyamines, polyurethanes,polyureas, polyaminotriazines, poly(meth)acrylates,poly(meth)acrylamides and copolymers thereof containing radicals of thistype.

The compounds of the following formulae in which m is a number from 2 toabout 200 are examples of 2,2,6,6-polyalkylpiperidine light stabilizersof this class. ##STR60##

Of these classes of compounds, classes a), d), e) and f) areparticularly suitable, in particular the Compounds Nos. 10, 13, 14, 23,24, 28, 29, 45, 47, 48, 63, 65, 69, 75, 77, 81, 84, 92 and 93.

Examples of organic materials which can be stabilized with the mixtureof (a) and (b) or with a compound of the formula Ia are fats, waxes,oils, cosmetics or photographic materials, but particularly organicpolymers. The following classes are examples of polymers of this type:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, polymethylpent-1-ene, polyisoprene orpolybutadiene, and polymerizates of cycloolefins, for examplecyclopentene or norbornene; and also polyethylene (which can, ifdesired, be crosslinked), for example high-density polyethylene (HDPE),low-density polyethylene (LDPE) and linear low-density polyethylene(LLDPE).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene or of polypropylene with polyethylene(for example PP/HDPE or PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with one another or withother vinyl monomers, for example ethylene/propylene copolymers, linearlow-density polyethylene (LLDPE) and mixtures thereof with low-densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acidcopolymers and salts thereof (ionomers), and also terpolymers ofethylene with propylene and a diene, such as hexadiene,dicyclopentadiene or ethylidenenorbornene; and also mixtures of suchcopolymers with one another and with polymers mentioned under 1), forexample polypropylene/ethylene/propylene copolymers, LDPE-ethylene/vinylacetate copolymers, LDPE-ethylene/acrylic acid copolymers,LLDPE-ethylene/vinyl acetate copolymers and LLDPE-ethylene/acrylic acidcopolymers.

3a. Hydrocarbon resins (for example C₅ -C₉), including hydrogenatedmodifications thereof (for example tackifying resins).

4. Polystyrene, poly-(p-methylstyrene) and poly-(α-methylstyrene).

5. Copolymers of styrene or α-methyistyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,styrene/maleic anhydride or styrene/acrylonitrile/methyl acrylate;mixtures of high impact resistance formed from styrene copolymers andanother polymer, for example a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer; and block copolymers of styrene,for example styrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene-butylene/styrene or styrene/ethylene-propylene/styrene.

6. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene/styrene orpolybutadiene/acrylonitrile copolymers, styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene, styrene and maleimide on polybutadiene, styrene andalkyl acrylates or alkyl methacrylates on polybutadiene, styrene andacrylonitrile on ethylene/propylene/diene terpolymers, styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers and mixtures thereofwith the copolymers mentioned under 5), such as are known, for example,as so-called ABS, MBS, ASA or AES polymers.

7. Halogen-containing polymers, for example polychloroprene, chlorinatedrubber, chlorinated or chlorosulfonated polyethylene, copolymers ofethylene and chlodnated ethylene, epichlorohydrin homopolymers andcopolymers, in particular polymers formed from halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride or polyvinylidene fluoride; and copolymers thereof,such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetateor vinylidene chloride/vinyl acetate.

8. Polymers derived from α,β-unsaturated acids and derivatives thereof,such as polyacrylates and polymethacrylates, polyacrylamides andpolyacrylonitriles.

9. Copolymers of the monomers mentioned under 8) with one another orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate copolymers, acrylonitrile/vinylhalide copolymers or acrylonitrile/alkyl methacrylate/butadieneterpolymers.

10. Polymers derived from unsaturated alcohols and amines or acylderivatives or acetals thereof, such as polyvinyl alcohol, polyvinylacetate, stearate, benzoate or maleate, polyvinylbutyral, polyallylphthalate or polyallylmelamine; and copolymers thereof with olefinsmentioned in item 1.

11. Homopolymers and copolymers of cyclic ethers, such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

12. Polyacetals, such as polyoxymethylene, and also polyoxymethylenes ofthis type containing comonomers, for example ethylene oxide, andpolyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

13. Polyphenylene oxides and sulfides and mixtures thereof with styrenepolymers or polyamides.

14. Polyurethanes derived from polyethers, polyesters and polybutadieneshaving terminal hydroxyl groups on the one hand and from aliphatic oraromatic polyisocyanates on the other hand, and also precursors thereof.

15. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12 or 4/6,polyamide 11, polyamide 12 and aromatic polyamides formed from m-xylene,aliamine and adipic acid; and polyamides prepared fromhexamethylenediamine and isophthalic and/or terephthalic acid and, ifappropriate, an elastomer as modifier, for examplepoly-2,4,4-trimethylhexamethyleneterephthalamide orpoly-m-phenyleneisophthalamide. Block copolymers of the polyamidesmentioned above with polyolefins, olefin copolymers, ionomers orchemically attached or grafted elastomers; or with polyethers, forexample polyethylene glycol, polypropylene glycol or polytetramethyleneglycol. Also polyamides or copolyamides modified with EPDM or ABS; andpolyamides which have been condensed during processing ("RIM polyamidesystems").

16. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.

17. Polyesters derived from dicarboxylic acids and dialcohols and/orfrom hydroxycarboxylic acids or the corresponding lactones, such aspolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates andblock polyether esters derived from polyethers having hydroxyl endgroups; and also polyesters modified with polycarbonates or MBS.

18. Polycarbonates and polyester carbonates.

19. Polysulfones, polyether sulfones and polyether ketones.

20. Crosslinked polymers derived from aldehydes on the one hand andphenols, urea or melamine on the other hand, such asphenol/formaldehyde, urea/formaldehyde and melamine/formaldehyde resins.

21. Drying and non-drying alkyd resins.

22. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols, and alsovinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

23. Crosslinkable acrylic resins derived from substituted acrylic acidesters, for example from epoxyacrylates, urethane acrylates or polyesteracrylates.

24. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, polyisocyanates or epoxy resins.

25. Crosslinked epoxy resins derived from polyepoxides, for example frombis-glycidyl ethers or cycloaliphatic diepoxides.

26. Natural polymers, such as cellulose, natural rubber, gelatine andthe polymer-homologously chemically modified derivatives thereof, suchas cellulose acetates, propionates and butyrates or the celluloseethers, such as methylcellulose; and also colophony resins andderivatives.

The use of the compounds according to the invention in coatings of alltypes is particularly preferred. These can be pigmented or unpigmentedcoatings or metal effect coatings. They can contain an organic solventor can be solvent-free or can be aqueous coatings.

The coatings can contain, as a binder, at least one of the polymerslisted above. The following are examples of coatings containing specialbinders:

1. Coatings based on cold-crosslinkable or hot-crosslinkable alkyd,acrylate, polyester, epoxy or melamine resins or mixtures of suchresins, if desired with an added acid curing catalyst;

2. Two-component polyurethane coatings based on acrylate, polyester orpolyether resins containing hydroxyl groups, and on aliphatic oraromatic polyisocyanates;

3. One-component polyurethane coatings based on masked polyisocyanateswhich are unmasked during baking;

4. Two-component coatings based on (poly)ketimines and aliphatic oraromatic polyisocyanates;

5. Two-component coatings based on (poly)ketimines and an unsaturatedacrylate resin or a polyacetoacetate resin or a methylmethacrylamidoglycolate;

6. Two-component coatings based on polyacrylates and polyepoxidescontaining carboxyl or amino groups;

7. Two-component coatings based on acrylate resins containing anhydridegroups, and on a polyhydroxyl or polyamino component;

8. Two-component coatings based on (poly)oxazolidines and acrylateresins containing anhydride groups, or unsaturated acrylate resins oraliphatic or aromatic polyisocyanates;

9. Two-component coatings based on unsaturated polyacrylates andpolymalonates;

10. Thermoplastic polyacrylate coatings based on thermoplastic acrylateresins or extraneously crosslinking acrylate resins in combination withetherified melamine resins;

11. Coating systems based on siloxane-modified or silane-modified orfluorine-modified acrylate resins.

The coatings can also be radiation-curable. In this case the binder iscomposed of monomeric or oligomeric compounds which contain ethylenicdouble bonds and are converted into a crosslinked, high-molecular formby irradiation with actinic light or with electron beams. In most casesthe binder is a mixture of such compounds. In radiation-curable coatingsthe compounds of formula I can be used also in absence of a stericallyhindered amine.

The coatings can be applied as one-coat or two-coat systems, it beingpreferable to add the stabilizers according to the invention to theunpigmented top coat.

The coatings can be applied to the substrates (metal, plastic, wood,etc.) by the customary processes, for example by brushing, spraying,curtain-coating, dipping or electrophoresis.

The amount of (a) and (b) added depends on the substrate and therequirements for its stability. In general, 0.01 to 5% by weight, inparticular 0.02 to 2% by weight, of the component (a) and 0.02 to 5% byweight, in particular 0.05 to 3% by weight, of the component (b) areadded, relative to the polymer.

The two components can be added on their own or as a mixture. Additionis preferably carried out before or during the shaping of the polymer.It can also be carried out as early as the preparation of the polymer,for example before or during polymerization.

The compounds of the formula Ia can also be used on their own, ie.without a sterically hindered amine, for stabilizing organic polymers.In this case 0.01 to 10% by weight, for example, preferably 0.05 to 5%by weight, of a compound of the formula Ia is added to the polymer. Theuse of compounds of the formula Ia as a stabilizer for polycarbonates isof particular interest.

In addition to the stabilizers, according to the invention, of theformula Ia or the stabilizer combination (a)+(b), it is also possible toadd other stabilizers to the polymer. The following axe examples ofthese:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-di-cyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol-2,4,6-triclycohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol and 2,6-di-nonyl-4-methylphenol.

1.2. Alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone and 2,6-diphenyl-4-octadecyloxyphenol.

1.3. Hydroxylated thiodiphenyl ethers, for example2,2'-thiobis-(6-tert-butyl-4-methylphenol),2,2'-thiobis-(4-octylphenol),4,4'-thiobis-(6-tert-butyl-3-methylphenol),4,4'-thiobis-(6-tert-butyl-2-methylphenol).

1.4. Alkylidene bisphenols, for example2,2'-methylenebis-(6-tert-butyl-4-methylphenol),2,2'-methylenebis-(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis-4-methyl-6-(α-methylcyclohexyl)-phenol!,2,2'-methylenebis-(4-methyl-6-cyclohexylphenol),2,2'-methylenebis-(6-nonyl-4-methylphenol),2,2'-methylenebis-(4,6-di-tert-butylphenol),2,2'-ethylidenebis-(4,6-di-tert-butylphenol),2,2'-ethylidenebis-(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis-6-(α-methylbenzyl)-4-nonylphenol!, 2,2'-methylenebis-6-(α,α-dimethylbenzyl)-4-nonylphenol!,4,4'-methylenebis-(2,6-di-tert-butylphenol),4,4'-methylenebis-(6-tert-butyl-2-methylphenol),1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane,2,6-bis-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane,1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis-3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyratel!,bis-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene and bis-2-(3'-tert-butyl-2-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl!terephthalate.

1.5. Benzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,bis-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-dithiol terephthalate,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, the Ca salt ofmonoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.6. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide,2,4-bis-(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazineand octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.

1.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid,with monohydric or polyhydric alcohols, for example methanol,octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol,diethylene glycol, triethylene glycol, pentacrythritol,tris-(hydroxyethyl) isocyanurate and N,N'-bis-(hydroxyethyl)oxamide.

1.8. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acidwith monohydric or polyhydric alcohols, for example methanol,octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol,diethylene glycol, triethylene glycol, pentaerythritol,tris-(hydroxyethyl) isocyanurate and N,N'-bis-(hydroxyethyl)oxamide.

1.9. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)-propionic acid withmonohydric or polyhydric alcohols, for example methanol, octadecanol,1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris-(hydroxyethyl)isocyanurate and N,N'-bis-(hydroxyethyl)oxamide.

1.10. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid,for exampleN,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine,N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamineand N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.

2. UV Absorbers and Light Stabilizers

2.1.2-(2'-hydroxyphenyl)-benzotriazoles, for example the 5'-methyl-,3',5'-di-tert-butyl- , 5'-tert-butyl-,5'-(1,1,3,3-tetramethylbutyl)-,5-chloro-3',5'-di-tert-butyl-, 5-chloro-3'-tert-butyl-5'-methyl-,3'-sec-butyl-5'-tert-butyl-, 4'-octoxy-, 3',5'-di-tert-amyl-,3',5'-bis-(α,α-dimethylbenzyl)-derivative.

2.2.2-Hydroxybenzophenones, for example the 4-hydroxy-, 4-methoxy-,4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2',4'-trihydroxy-or 2'-hydroxy-4,4'-dimethoxy-derivative.

2.3. Esters of unsubstituted or substituted benzoic acids, for example4-tert-butylphenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol,benzoylresorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl or isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl orbutyl α-cyano-β-methyl-p-methoxycinnamate, methylα-carbomethoxy-p-methoxycinnamate orN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of 2,2'-thiobis-4-(1,1,3,3-tetramethylbutyl)-phenol!, such as the 1:1 complex or the 1:2complex, if appropriate with additional ligands, such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of monoalkyl4-hydroxy-3,5-di-tert-butylbenzylphosphonates, such as the methyl orethyl ester, nickel complexes of ketoximes, such as2-hydroxy-4-methylphenyl undecyl ketoxime, or nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, if appropriate with additionalligands.

2.6. Oxamides, for example 4,4'-di-octyloxyoxanilide,2,2'-di-octyloxy-5,5'-di-tert-butyloxanilide,2,2'-di-dodecyloxy-5,5'-di-tert-butyloxanilide,2-ethoxy-2'-ethyloxanilide, N,N'-bis-(3-dimethylanminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2'-ethyloxanilide and a mixture thereof with2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide or mixtures of o-methoxy-and p-methoxy-disubstituted oxanilides and of o-ethoxy- andp-ethoxy-disubstituted oxanilides.

3. Metal deactivators, for example N,N'-diphenyloxamide,N-salicylal-N'-salicyloylhydrazine, N,N'-bis-(salicyloyl)-hydrazine,N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine,3-salicyloylamino-1,2,4-triazole and bis-(benzylidene)-oxalic aciddihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite,tetrakis-(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite and3,9-bis-(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro5.5!undecane.

5. Compounds which destroy peroxides, for example esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercaptobenzimidazole, the zinc salt of2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyldisulfide and pentaerythritol tetrakis-(β-dodecylmercapto)propionate.

6. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

7. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali and alkalineearth salts of higher fatty acids, for example Ca stearate, Zn stearate,Mg stearate, Na ricinoleate and K palmitate, antimony pyrocatecholate ortin pyrocatecholate.

8. PVC stabilizers, for example organotin compounds or salts of barium,cadmium, zinc and led.

Other materials such as are customary in the technology of plastics andpaints can also be added. Examples of these are fillers and reinforcingagents, pigments, dyes, plasticizers, solvents, lubricants, flow-controlagents, fluorescent brighteners, nucleating agents, antistatic agents orfire-retarding agents.

The invention also relates, therefore, to organic polymers containing,as stabilizers, a sterically hindered amine of the polyalkylpiperidinetype and a hydroxyphenyltriazine of the formula I, and also to organicpolymers containing a compound of the formula Ia as the stabilizer.

The polymers stabilized in this manner can be used in various shapes,for example as films, fibres, tapes, mouldings, profiles, latex,dispersions, paints or cements.

The following examples illustrate the invention in greater detailwithout intending to limit it to the examples. Pans and percentages areparts by weight and percentages by weight.

PREPARATION EXAMPLES Example 1

23.8 g (0.06 mol) of2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine(prepared as described in U.S. Pat. No. 3,244,708 Example 16) aresuspended in 300 ml of xylene. 12.1 g (0.09 mol) of 97% butyl glycidylether and 0.75 g (0.006 mol) of dimethylbenzylamine are added to thissuspension, and the mixture is heated to reflux temperature. After areaction time of 5 hours the clear, brownish solution is cooled andclarified by filtration through 100 g of silica gel. The yellow solutionis evaporated and the residue is recrystallized from hexane/toluene.This gives 27.3 g of pale yellow crystals of 2-2-hydroxy-4(3-butoxy-2-hydroxypropyloxy)-phenyl!-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin(=86% yield). Melting point: 80°-83° C. (Compound 1).

In analogous manner the compounds 2 to 28, listed in Table 1, areobtained from2-(2,4-dihydroxyphenyl!-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine andan epoxy compound.

                                      TABLE 1                                     __________________________________________________________________________     ##STR61##                                                                    Compound                                                                            n R.sub.7                             Physical data                     __________________________________________________________________________     1    1 CH.sub.2 CH(OH)CH.sub.2 OC.sub.4 H.sub.9                                                                          m.p. 80-83° C.              2    1 CH.sub.2 CH(OH)CH.sub.2 OCOC(CH.sub.3)CH.sub.2                                                                    m.p. 100-103° C.            3    2 CH.sub.2 CH(OH)CH.sub.2 O(CH.sub.2).sub.4 OCH.sub.2 CH(OH)CH.sub.2                                                m.p. 150-152° C.            4    1                                                                                ##STR62##                          m.p. 115-117° C.            5    1 CH.sub.2 CH(OH)CH.sub.2 OH          m.p. 165-167° C.            6    1                                                                                ##STR63##                          m.p. 101-104° C.            7    1                                                                                ##STR64##                          m.p. 75-77° C.              8    1                                                                                ##STR65##                          Oil found: C: 75.6% H:                                                              calc.: C: 75.9% H:                                                           9.1%                          9    2                                                                                ##STR66##                          m.p. 100-103° C.           10    1 CH.sub.2 CH(OH)(CH.sub.2).sub.11 CH.sub.3                                                                         m.p. 102-104° C.           11    1 CH.sub.2 CH(OH)(CH.sub.2).sub.7 CH.sub.3                                                                          m.p. 97-99° C.             12    1                                                                                ##STR67##                          Oil found: C: 64.0% H:  7.6%                                                  N:  4.4%                                                                              calc.: C: 66.7% H:                                                           7.16% N:  5.4%             13    1                                                                                ##STR68##                          Oil found: calc.:                                                                     N: 3.75% N: 3.43%         14    2                                                                                ##STR69##                          Oil found: calc.:                                                                     N: 5.17% N: 5.18%         15    1 CH.sub.2 CH(OH)CH.sub.2 OCOC.sub.9 H.sub.19                                                                       Oil                                                                           found: N: 6.3%                                                                calc.: N: 6.7%                    16    1                                                                                ##STR70##                          m.p. 152-155° C.           17    1 CH.sub.2 CH(OH)CH.sub.2 O(C.sub.13 H.sub.27 to C.sub.15 H.sub.31)                                                 Oil                                                                           MS, NMR                           18    1 CH.sub.2 CH(OH)CH.sub.2 O(C.sub.12 H.sub.25 to C.sub.14 H.sub.29)                                                 Oil                                                                           MS, NMR                           19    2                                                                                ##STR71##                          Resin found: C = 71.3%, H =                                                   6.6% calc.: C = 71.4%, H =                                                    6.6%                              20    1 CH.sub.2 CH(OH)CH.sub.2 OCOC.sub.10 H.sub.21 -tert.                                                               Resin                                                                         MS, NMR                           21    1 CH.sub.2 CH(OH)CH.sub.2 OCH.sub.2 CHCH.sub.2                                                                      m.p. 94-95° C.             22    1 CH.sub.2 CH(OH)CH.sub.3             m.p. 151-153° C.           23    1                                                                                ##STR72##                          m.p. 99-101° C.            24    2                                                                                ##STR73##                          Resin found: N = 8.2% calc.:                                                  N = 8.3%                          __________________________________________________________________________

Example 2

22.1 g (0.05 mol) of2-(2-hydroxy-4-hydroxyethoxy-phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine(prepared as described in U.S. Pat. No. 3,244,708, Example 18), aredissolved in 300 ml of tetrahydrofurane at 40° C. and 21 ml (0.15 mol)of triethylamine are added. A solution of 5.05 ml (0.053 mol) of acrylicacid chloride in 20 ml THF is added dropwise with stirring and withcooling the reaction mixture to 25°-30° C. After further stirring of twohours the precipitated ammonium salt is filtered off, the filtrate isevaporated and the residue recrystallized from toluene-hexane mixture toobtain 22 g (88.7% yield) of2-(2-hydroxy-4-acryloyloxyethoxy-phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazineas slightly yellow crystals (compound No. 25), m.p. 128°-129° C.

In analogous manner the compounds No. 26 and 27 were prepared.

    ______________________________________                                        Compound                                                                              n     R.sub.7            Phys. data                                   ______________________________________                                        25      1     --CH.sub.2 CH.sub.2 OCOCH═CH.sub.2                                                           m.p. 128-129° C.                      26      1     --CH.sub.2 CH(CH.sub.3)OCOCH═CH.sub.2                                                        m.p. 128-129° C.                      27      1     --CH.sub.2 CH.sub.2 OCOCH(CH.sub.3)═CH.sub.2                                                 m.p. 128-129° C.                      ______________________________________                                    

Example 3

20 g (0.04 mol) of2-(2-hydroxy-4-ethoxycarbonylmethoxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine(prepared as described in U.S. Pat. No. 3,244,708, Example 19), aredissolved in 100 ml of toluene, and 5 g (0.048 mol) of 2-methylpentanoland 0.5 g of dibutyltin oxide as catalyst are added, and the mixture isheated to reflux temperature. In the course of this a toluene/ethanolmixture is distilled off. The toluene is replenished dropwise from adropping funnel. The transesterification reaction is complete after 2hours. The solution is cooled and filtered through 80 g of silica geland is then evaporated. The residue is recrystallized from ethanol. Thisgives 14 g of the compound 28 (see Table 2). Melting point: 87°-89° C.

Compounds 29 to 37 are obtained analogously by transesterification withthe corresponding alcohols.

                                      TABLE 2                                     __________________________________________________________________________     ##STR74##                                                                    Compound                                                                            R.sub.8           Physical data                                         __________________________________________________________________________    28                                                                                   ##STR75##        m.p. 87-89° C.                                 29    CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                             m.p. 136-138° C.                               30    C.sub.8 H.sub.17 (isomer mixture)                                                               Waxlike                                                                       calcd.                                                                            C 74.05%                                                                           H 7.28%                                                                            N 7.4%                                                          found                                                                             C 73.98%                                                                           H 7.36%                                                                            N 7.3%                                  31                                                                                   ##STR76##        Oil calcd. found                                                                   C 64.47% C 64.75%                                                                  H 6.99% H 7.00%                                                                    N 5.50% N 5.72%                        32    C.sub.10 H.sub.21 (isomer mixture)                                                              Waxlike                                                                       calcd.                                                                            C 74.59%                                                                           H 7.61%                                                                            N 7.05%                                                         found                                                                             C 74.76%                                                                           H 7.73%                                                                            N 6.89%                                 33                                                                                   ##STR77##        Resin calcd. found                                                                 C 70.45% C 70.12%                                                                  H 7.06% H 7.02%                                                                    N 6.85% N 6.84%                        34                                                                                   ##STR78##        m.p. 75-78° C.                                 35    (CH.sub.2).sub.8 CHCH(CH.sub.2).sub.7 CH.sub.3                                                  Waxlike                                                                       calcd.                                                                            C 76.96%                                                                           H 8.42%                                                                            N 5.95%                                                         found                                                                             C 77.02%                                                                           H 8.47%                                                                            N 5.74%                                 36    (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OC.sub.6 H.sub.13                                            Resin                                                                         calcd.                                                                            C 70.68%                                                                           H 7.37%                                                                            N 6.68%                                                         found                                                                             C 70.53%                                                                           H 7.49%                                                                            N 6.39%                                 37                                                                                   ##STR79##        Resin calcd. found                                                                 C 63.44% C 63.54%                                                                  H 7.22% H 7.20%                                                                    N 4.93% N 5.01%                        __________________________________________________________________________

Example 4

9.1 g (0.02 mol) of2-(2-hydroxy-4-carboxymethoxy-phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine(prepared as described in U.S. Pat. No. 3,244,708, Example 16) aresuspended in 40 ml of thionyl chloride, and 1 ml of DMF is added. Themixture is heated at reflux temperature for 2 hours. A clear yellowsolution is formed with moderate evolution of gas. This solution isevaporated to give 9.5 g of4-(4,6-di-2',4'-xylyl-s-triazin-2-yl)-3-hydroxyphenoxy!-acetyl chloride(Compound 38). This acid chloride is dissolved in 100 ml of toluene.19.3 g (0.08 mol) of bis-(2-ethylhexyl)-amine are added dropwise at roomtemperature. The reaction proceeds exothermically from 22° C. to 40° C.The mixture is left for 1 hour at room temperature to complete thereaction. The product is then purified by column chromatography oversilica gel. This gives approx. 5 g of a pale yellow, highly viscous oil,4-(4,6-di-2',4'-xylyl-s-triazin-2-yl)-3-hydroxyphenoxy!-acetic acidbis-(2-ethylhexyl)-amide (Compound 39).

Calcd. C 76.07%, H 8.61%, N 8.25% Found. C 75.91%, H 8.46%, N 8.16%

Example 5

39.7 g (0.1 mol) of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine aredissolved in 250 ml of DMZF. 20.7 g of potassium carbonate are added tothis brownish solution. An orange suspension is formed. 17 g (0.052 mol)of 1,12-dibromododecane are added and the mixture is heated at 100° C.The reaction is complete after 2 hours. The cooled reaction solution isthen poured into 1.5 1 of water, and the precipitate is filtered off andwashed with 2-3 times 100-200 ml of H₂ O. The crystals are thenrecrystallized from xylene. Melting point: 158°-163° C. (Compound 40).

Compounds 41 and 42 are obtained analogously, using 1,6-dibromohexane,1,4-dichloro-2-butene and p-xylylenedibromid.

                  TABLE 3                                                         ______________________________________                                         ##STR80##                                                                    Compound R.sub.7            Physical data                                     ______________________________________                                        40       (CH.sub.2).sub.12  m.p. 158-163° C.                           41       (CH.sub.2).sub.6   m.p. 203-205° C.                           42       CH.sub.2 CHCHCH.sub.2                                                                            m.p. 230-235° C.                           43                                                                                      ##STR81##         m.p. 252-254° C.                           ______________________________________                                    

Example 6

20 g (0.05 mol) of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine aresuspended in 100 ml of toluene, and 100 ml of 1N NaOH and 1 g oftetrabutylammonium bromide are added. The mixture is heated for 10minutes at 80° C. and then cooled, to give a yellow paste. 12.3 ml (0.15mol) of epibromohydrin are added to this paste and the mixture is againheated for 6 hours at 50° C. When the reaction is complete, methylenechloride is added to the organic phase, which is separated off from theaqueous phase and filtered through Hyflo. It is then evaporated and thecrystalline residue is recrystailized from toluene. This gives 14 g ofpale yellow crystals,2-(2-hydroxy-4-glycidyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine(Compound 44), melting point 152°-155° C.

Example 7

9.07 g (0.02 mol) of Compound 44 and 7.95 g (0.02 mol) of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine aresuspended in 150 ml of xylene. 0.2 g of dimethylaminopyridine are addedand the mixture is heated at reflux temperature. The reaction iscomplete after 4 hours. The mixture is diluted with 200 ml of tolueneand cooled. In the course of this the product is precipitated. It isfiltered off and purified further by recrystallization from toluenetogether with a little Fuller's earth. This gives 9.1 g of pale beigecrystals, 1,3-bis-{4-4,6-di-(2,4-dimethylphenyl)-s-triazine-2-yl!-3-hydroxy-phenoxy}-2-hydroxypropane(Compound 45), melting point: 222°-224° C.

Example 8

18.5 g (0.05 mol) of2-(2,4-dihydroxyphenyl)-4,6-bis-(4-methylphenyl)-1,3,5-triazine (Helv.Chim. Acta 55, 1566 (1972)) and 3.9 g (0.05 mol) of potassium methoxideare suspended in 200 ml of anhydrous n-butanol, and 7.4 g (0.06 mol) ofbutyl chloroacetate are added dropwise between 50° C. and 100° C. After17 hours under reflux the solvent is evaporated and the crude product iswashed with water, dried and recrystallized from petroleum ether(boiling point 110° C.-140° C.) (Compound No. 46).

Melting point: 142°-146° C. Calcd. C 72.03 H 6.04N 8.69% Found C 71.88 H6.01N 8.81% ##STR82##

Example 9

A) 55.4 g (0.15 mol) of2-(2,4-dihydroxyphenyl)-4,6-bis-(4-methylphenyl)-1,3,5-triazine aredissolved in refluxing 2-butanone (11) in the presence of 27.6 g (0.2mol) of K₂ CO₃. A catalytic amount (0.2 g) of KI is added, and 36.8 g(0.3 mol) of ethyl chloroacetate are added dropwise over 1 h30. Afterrefluxing for 25 h, the reaction mixture is cooled in ice, theprecipitate is filtered off, washed with water to neutrality and thenwith methanol. Drying in the oven yields the analytically pure2-(2-hydroxy-4-ethoxycarbonylmethoxyphenyl)-4,6-bis-(4-methylphenyl)-1,3,5-triazine(54 g, m.p. 166°-167° C.) (Compound No. 47).

B) 11.4 g (0.025 mol) of compound 47 and 3.9 g (0.03 mol) of octanol(isomeric mixture) are refiuxed in 120 ml xylene for 22 h in thepresence of 0.62 g (2.5 mmol) of dibutyltinoxide. During the reaction axylene/ethanol mixture is distilled off, the xylene being replenisheddropwise from a dropping funnel. The reaction mixture is cooled to 40°C., filtered through a pad of Prolith and evaporated. Drying at 100°C./0.01 mmHg affords the transesterification product as a viscous yellowoil (12.5 g) that solidifies to a wax (Compound No. 48).

Calcd. C=73.44%, H=6.91%, N=7.79% Found C=72.95%, H=6.70%, N=7.48%

Compounds No. 49 to 52 (Table 4) are obtained analogously bytransesterification with the corresponding alcohols.

                  TABLE 4                                                         ______________________________________                                         ##STR83##                                                                    Compound                                                                              n      R.sub.8          Physical data                                 ______________________________________                                        49      1      CH.sub.2 CH.sub.2 OCH.sub.3                                                                    m.p. 150-153° C.                       50      2      CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                          m.p. 118-121° C.                       51      1      (CH.sub.2).sub.6 m.p. 235-238° C.                       52      4                                                                                     ##STR84##       m.p. 219-231° C.                       ______________________________________                                    

Example 10

40.6 g (0.11 mol) of2-(2,4-dihydroxyphenyl)-4,6-bis-(4-methylphenyl)-1,3,5-triazine aredissolved in refluxing 2-butanone (500 ml) in the presence of 20.7 g(0.15 mol) of K₂ CO₃. 18.1 g (0.055 mol) of 1,12-dibromodecane dissolvedin 100 ml of 2-butanone are added dropwise over 3 h and the mixture isrefluxed for 35 h. In the course of this, precipitation of the finalproduct occurs. The reaction mixture is cooled in ice, the precipitateis filtered off, washed with water to neutrality and then with methanol.Drying in the oven affords 46.2 g of the analytically pure compound No.53 (Table 5). Off-white solid, m.p. 219°-220° C.

Analogous treatment with 1,6-dibromohexane or epibromohydrin givescompounds No. 54 and 55 (Table 5).

                                      TABLE 5                                     __________________________________________________________________________     ##STR85##                                                                    Compound                                                                            n R.sub.7                        Physical data                          __________________________________________________________________________    53    2 (CH.sub.2).sub.12              m.p. 219-220° C.                54    2 (CH.sub.2).sub.6               m.p. 247-249° C.                55    1                                                                                ##STR86##                     m.p. 205-208° C.                56    1                                                                                ##STR87##                     m.p. 166-167° C.                57    1                                                                                ##STR88##                     m.p. 123-125° C.                58    1                                                                                ##STR89##                     Yellow oil calc. C 66.02% H  6.89%                                              5.63%                                                                             found 64.52%  6.98%  5.23%       59    1                                                                                ##STR90##                     m.p. 183-185° C.                60    1                                                                                ##STR91##                     m.p. 135-138° C.                61    2 OC(CH.sub.2).sub.8 CO          m.p. 220-228° C.                __________________________________________________________________________

Example 11

A mixture of 14.8 g (0.04 mol) of2-(2,4-dihydroxyphenyl)-4,6-bis-(4-methylphenyl)-1,3,5-triazine, 10.4 g(0.08 mol) of butylglycidylether and 2.1 g (6.5 mmol) oftetratabutylammoniumbromide is refluxed in 150 ml of 2-butanone during85 h. The reaction mixture is cooled in ice, the precipitate is filteredoff, washed with water and methanol, and dried in the oven. This yields17.5 g of a pale yellow solid, m.p. 166°-167° C. (Compound No. 56, Table4).

Analogous treatment with the corresponding glycidyl ethers or estersyields the compounds 57 to 60 (Table 4).

Example 12

A solution of 3.6 g (0.015 mol) of sebacyl chloride in 10 ml toluene isadded dropwise at 10° C. to a solution of2-(2,4-dihydroxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazinc and 3.3 g(0.033 mol) of triethylamine in 100 ml toluene and 50 ml of DMF. After50 h at room temperature, the reaction mixture is diluted with water,filtered, the precipitate is washed with water, methanol and chloroform,and dried in the oven. 8.7 g of the diester 61 (Table 4) are obtained asa pale beige solid, m.p. 220°-228° C.

Example 13

When 20.5 g (0.06 mol) of2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine are treated with22.8 g (0.12 mol) of 2-ethylhexyl glycidyl ether analogously to example11, 23.3 g of the pale yellow compound No. 62 (m.p. 116° to 118° C.) areobtained. ##STR92##

Example 14

7.9 g (0.02 mol) of2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 5.7g (0.02 mol) of a technical mixture of dodecyl, tridecyl and tetradecylglycidyl ethers (Araldite® DY 025) and 0.15 g of ethyltriphenylphosphonium iodide in 50 ml of mesitylene are heated at160°-165° C. for 10 hours, with stirring. The reaction solution iswashed with water, dried over MgSO₄, and filtered. The filtrate isstirred for 2 hours with 2 g of Filtrol 4, filtered and evaporated invacuo. The residue is freed from residual mesitylene at 120° C. and 0.01mmHg. This leaves 12.1 g of an oil (Compound No. 63).

C₄₁ H₅₅ N₃ O₄ Calcd. C75.30 H8.48 N6.43% Found. C75.0 H8.1N 6.8%

APPLICATION EXAMPLES Example 15

Stabilization of a 2-Coat Metallic Coating

A clear lacquer is prepared by mixing the following components:

    ______________________________________                                        59.2 Parts of a commercial acrylic resin (Uracron ® XB 2263, DMS               Resins BV, NL) which is a 50% solution in xylene,                        11.6 parts of a 90% melamine resin (Cymel ® 327, Amer. Cyanamid                Corp.)                                                                   19.4 parts of xylene                                                          5.5  parts of butylgylcol acetate                                             9.3  parts of butanol                                                         1.0  part of a levelling agent (Baysilon ® A, Bayer AG) which is a             1% solution in xylene                                                    100  parts lacquer containing 40% solids.                                     ______________________________________                                    

Samples of this lacquer are mixed with 0.5% (related to the solids) ofdi(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate (=HA-1) and 1,5%(related to the solids) of a triazine stabilizer listed in table 6.

The clear lacquer is diluted to a sprayable state with a mixture of13:6:1 xylene/butanol/butyl glycol acetate and is sprayed onto apreviously prepared aluminum sheet (coil-coated and primed with asilver-metallic paint based on polyester/celluloseacetobutyrate/melamine resin), and the sheet is baked for 30 minutes at130° C. This results in a dry film thickness of 40-50 μm of clearlacquer. A clear lacquer containing no light stabilizer is used as acomparison.

The samples are exposed in a UVCON, Type UVB-313, weathering equipmentwith a cycle of 8 hrs of dry UV irradiation at 70° C. and 4 hrs ofcondensation at 50° C. The 20°-gloss of the samples is measured incertain intervals of weathering time using the method of DIN 67530. Theresults are given in Table 6.

                  TABLE 6                                                         ______________________________________                                        Piperidin                                                                             Triazine Stabilizer                                                                        20°-Gloss after exposure of                       Stabilizer                                                                            (Compound No.)                                                                             0     1600 3200 4800 6400 hrs                            ______________________________________                                        --      --               86  31   --   --   --                                0.5% HA-1                                                                             1.5%     1       86  79   74   77   61                                0.5% HA-1                                                                             1.5%     30      86  74   68   66   57                                0.5% HA-1                                                                             1.5%     32      82  69   72   68   59                                0.5% HA-1                                                                             1.5%     33      85  79   74   72   64                                ______________________________________                                    

Example 16

The preparation of the samples and their testing is the same as inExample 15. As comparison C-1 and C-2, two triazine derivatives knownfrom U.S. Pat. No. 4,619,956, are used as triazine stabilizers.

C-1=2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-diphenyl-1,3,5-triazine

C-2=2-(2-hydroxy-4-octadecyloxyphenyl)-4,6-diphenyl-1,3,5-triazine

The results are shown in Table 7.

                  TABLE 7                                                         ______________________________________                                        Piperidin              20°-Gloss after exposure of                     Stabilizer                                                                             Triazine Stabilizer                                                                         0      1600 3200 4000 hrs                              ______________________________________                                        --       --                84   19   --   --                                  0.5% HA-1                                                                              1.5%   Compound 34                                                                              84   80   78   59                                  0.5% HA-1                                                                              1.5%   Compound 35                                                                              85   81   80   75                                  0.5% HA-1                                                                              1.5%   Compound 36                                                                              85   80   78   76                                  0.5% HA-1                                                                              1.5%   Compound 37                                                                              85   80   79   77                                  0.5% HA-1                                                                              1.5%   Compound 39                                                                              85   81   72   74                                  0.5% HA-1                                                                              1.5%   C-1        85   54   35   37                                  0.5% HA-1                                                                              1.5%   C-2        79   38   34   37                                  ______________________________________                                    

Example 17

A similar clear lacquer is prepared from

    ______________________________________                                        54.5        parts of Uracron ® XB 2263                                    16.3        parts of Cymel ® 327                                          19.4        parts of xylene                                                   5.5         parts of butylgylcol acetate                                      3.3         parts of butanol                                                  1           part of Baysilon ® A                                          100         parts lacquer containing 41.5% solids.                            ______________________________________                                    

Samples of this lacquer are mixed with 0.5% (related to the solids) ofHA-1 and 1.5% (related to the solids) of a triazine stabilizer listed inTable 8. The lacquer is diluted to a sprayable state by diluting with a13:6:1 mixture of xylene/butanol/butylglycol acetate and is sprayed ontoan aluminium sheet which is coil coated and primed with a metallic bluecommercial paint (Glasomax®, Glasurit GmbH, Munster). Mter baking for 30minutes at 130° C. the clear lacquer layer has a thickness of 40-45 μm.

The samples are weathered in a UVCON, Type UVB 313, as described inExample 15 and the 20°-gloss of the weathered samples is measuredaccording to method DIN 67530. The results are shown in Table 8.

                  TABLE 8                                                         ______________________________________                                        Piperidin                                                                              Triazine Stabilizer                                                                        20°-Gloss after exposure of                      Stabilizer                                                                             (Compound No.)                                                                             0      800  1600  2000 hrs                              ______________________________________                                        --       --               85   75   42      20-                               0.5% HA-1                                                                              1.5%     4       86   80   78    78                                  0.5% HA-1                                                                              1.5%     6       87   81   81    81                                  0.5% HA-1                                                                              1.5%     7       85   81   81    79                                  0.5% HA-1                                                                              1.5%     10      86   82   80    80                                  0.5% HA-1                                                                              1.5%     11      86   81   81    78                                  0.5% HA-1                                                                              1.5%     17      86   81   81    81                                  0.5% HA-1                                                                              1.5%     18      87   81   80    80                                  0.5% HA-1                                                                              1.5%     62      84   80   78    81                                  ______________________________________                                    

Example 18

The two-coat samples are prepared as described in Example 15, however,no piperidin stabilizer is added. The samples are weathered in aWeatherometer with cycle CAM 159 and with using an edge filter of typeA. Measured is the 20°-gloss before and after exposure, the results areshown in Table 9.

                  TABLE 9                                                         ______________________________________                                        Triazine Stabilizer                                                                        20°-Gloss after exposure of                               (Compound No.)                                                                             0          2000   3600 hrs                                       ______________________________________                                        none         85         47     25                                             34           86         71     64                                             35           86         72     61                                             36           86         73     60                                             ______________________________________                                    

Example 19

The two-coat samples are prepared as described in Example 17, however,no piperidin stabilizer is added. The samples are weathered in a UVCON,type UVB-313 with cycle of 8 hrs of UV irradiation at 70° C. and 4 hrsof condensation at 50° C. The 20°-gloss of the sample is measuredaccording to method DIN 67530 before and after exposure. Further thechange of colour shade ΔE after exposure is measured according to methodDIN 6174. The results are shown in Table 10.

                  TABLE 10                                                        ______________________________________                                                      20°-Gloss after                                          Triazine Stabilizer                                                                         exposure of     ΔE                                        (Compound No.)                                                                              0     800      1600 hrs                                                                             after 1600 h                              ______________________________________                                        none          85    75       42     6.6                                        6            84    80       80     1.3                                        7            84    81       80     1.3                                       17            86    81       80     1.6                                       18            86    81       80     1.4                                       62            86    82       81     1.0                                       ______________________________________                                    

Example 20

Stabilization of a radiation-curable system A clear lacquer is preparedby mixing 14 parts of tris(2-acryloyloxyethyl)isocyanurate with 6 partsof 1,6-hexanediol diacrylate and 0.4 parts of 1-benzoylcyclohexanol (asphotoinitiator). A triazine stabilizer is added in an amount of 1.5%.The lacquer is coated to a white coil-coated aluminium sheet in adry-thickness of about 40 μm.

The samples are hardened by UV irradiation in a PPG processor (2×80W/cm, 2×10 m (min) and weathered in a UVCON, type UVB-313 with a cycleof 4 hours of UV irradiation at 60° C. and 4 hrs of condensation at 50°C.

The yellowness index (method ASTM D 1925-70) of the samples is measuredbefore and after the exposure. The results are shown in Table 11.

                  TABLE 11                                                        ______________________________________                                        Triazine Stabilizer                                                                         Yellowness Index after exposure of                              (Compound No.)                                                                              0      200       400  600 hrs                                   ______________________________________                                        none              -1.0   19.6    28.0 35.3                                    1.5%     17       -0.6   1.8     1.8  2.1                                     ______________________________________                                    

What is claimed is:
 1. A composition comprising:(a) an organic materialselected from the group consisting of organic polymers, fats, waxes,oils, cosmetics, and photographic material, which organic material isstabilized against damage caused by light, heat, and oxygen by thepresence of (b) at least one sterically hindered amine of thepolyalkylpiperidine type, and (c) at least oneo-hydroxyphenyl-s-triazine of the formula: ##STR93## wherein: R1 isalkyl of 1 to 12 carbon atoms;R2 is alkyl of 1 to 12 carbon atoms; R3 isalkyl of 1 to 12 carbon atoms; R4 is alkyl of 1 to 12 carbon atoms; andR7 is:(i) alkoxy of 1 to 12 carbon atoms substituted with hydroxy; or(ii) alkoxy of 1 to 12 carbon atoms which is substituted with alkoxy of1-18 carbon atoms and hydroxy.
 2. A composition according to claim 1wherein each of R₁, R₂, R₃, and R₄ is methyl and R₇ is --OCH₂ CH(OH)CH₂OR in which R is an alkyl of 1 to 18 carbon atoms.
 3. A compositionaccording to claim 2 wherein R is butyl.
 4. A composition according toclaim 2 wherein R is octyl.
 5. A composition according to claim 2wherein R is alkyl of 12-14 carbon atoms.
 6. A composition according toclaim 1 wherein in said o-hydroxyphenyl-s-triazine, each of R₁, R₂, R₃,and R₄ is methyl.
 7. A composition according to claim 1, wherein saidsterically hindered amine containing at least one group of the formula:##STR94## in which R is hydrogen or methyl.
 8. A composition accordingto claim 7, wherein R is hydrogen.
 9. A composition according to claim7, wherein said sterically hindered amine is (i)di-(2,2,6,6-tetramethylpiperidin-4-yl) succinate; (ii)di-(2,2,6,6-tetramethylpiperidin-4-yl) sebacate; (iii)di-(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate; (iv) di-(1,2,2,6,6-pentamethylpiperidin-4-yl)butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)-malonate; (v)di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; (vi)tetra-(2,2, 6,6-tetramethylpiperidin-4-yl)butane-1,2,3,4-tetracarboxylate; (vii)tetra-(1,2,2,6,6-pentamethylpiperidin-4-yl)butane-1,2,3,4-tetracarboxylate; (viii)N-(2,2,6,6-tetramethylpiperidin-4-yl)-β-aminopropionic acid dodecylester; (ix)N-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-N'-dodecyl-oxalamide;(x) N-(2,2,6,6-tetramethylpiperidin-4-yl)-α-dodecylsuccinimide; (xi)2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro5.1.11.2!heneicosane; (xii)8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspirol4.5!decane-2,4-dione; (xiii)20-(dodecyloxycarbonylethyl)-2,2,4,4-tetramethyl-7-oxa-3,20-diaza-221-oxo-dispiro-5.1.11.2!heneicosane; (xiv) a compound of the formula: ##STR95## inwhich R is ##STR96## (xv) a compound of the formula: ##STR97## in whichR is ##STR98## (xvi) a compound of the formula: ##STR99## (xvii) acompound of the formula: ##STR100## (xviii) a compound of the formula:##STR101## (xix) a compound of the formula: ##STR102## in which m has avalue of from 2 to about
 200. 10. A composition according to claim 1which contains 0.01 to 5% by weight of said sterically hindered amineand 0.02 to 5% by weight of said o-hydroxyphenyl-s-triazine, relative tosaid organic material.
 11. A composition according to claim 10 whichcontains 0.02 to 2% by weight of said sterically hindered amine and 0.05to 3% by weight of said o-hydroxyphenyl-s-triazine.
 12. A compositionaccording to claim 1 wherein the organic material is an organic polymer.13. A composition according to claim 12, which, in addition to saidsterically hindered amine and said o-hydroxyphenyl-s-triazine alsocontains further stabilizers, fillers, reinforcing agents, pigments,dyes, plasticizers, solvents, lubricants, flow-control agents,fluorescent brighteners, nucleating agents, antistatic agents orfire-retarding agents.
 14. A composition according to claim 12, whereinthe polymer is a coating binder.
 15. A composition according to claim 1,wherein the material is a radiation-curable coating material.
 16. Aprocess for stabilizing an organic material selected from the groupconsisting of organic polymers, fats, waxes, oils, cosmetics andphotographic materials against damage caused by exposure to light, heatand oxygen, which comprises incorporating into said organic material aneffective stabilizing amount of at least one sterically hindered amineof the polyalkylpiperidine type and at least oneo-hydroxyphenyl-s-triazine of the formula: ##STR103## wherein: R₁ isalkyl of 1 to 12 carbon atoms;R₂ is alkyl of 1 to 12 carbon atoms; R₃ isalkyl of 1 to 12 carbon atoms; R₄ is alkyl of 1 to 12 carbon atoms; andR₇ is:(i) alkoxy of 1 to 12 carbon atoms substituted with hydroxy; or(ii) alkoxy of 1 to 12 carbon atoms which is substituted with alkoxy of1-18 carbon atoms and hydroxy.
 17. The process of claim 16, wherein saidorganic material is an organic polymer.
 18. The process of claim 17,wherein said organic polymer is a polycarbonate.
 19. The process ofclaim 17, wherein said organic polymer is a radiation-curable coatingmaterial.